CN113198433A - Molecular sieve and porous organic polymer core-shell structure composite adsorbent and preparation method thereof - Google Patents
Molecular sieve and porous organic polymer core-shell structure composite adsorbent and preparation method thereof Download PDFInfo
- Publication number
- CN113198433A CN113198433A CN202110338859.3A CN202110338859A CN113198433A CN 113198433 A CN113198433 A CN 113198433A CN 202110338859 A CN202110338859 A CN 202110338859A CN 113198433 A CN113198433 A CN 113198433A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mixed solution
- stirring
- composite adsorbent
- organic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of adsorbents, and designs a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent. The method comprises the following specific steps: (1) weighing organosilane and dissolving in an organic solvent, and then adding a molecular sieve with certain mass; (2) weighing benzyl chloride, dissolving the benzyl chloride in an organic solvent, and adding an organic cross-linking agent to obtain a mixed solution B; mixing the solution B; (3) dropwise adding the mixed solution B into the mixed solution A, and adding a certain amount of anhydrous aluminum chloride to obtain a mixed solution C; (4) and naturally cooling the mixed solution C to room temperature, filtering and recovering a solid-phase product, and drying in vacuum to obtain the product. The synthesis method is simple and easy to operate; the synthesized molecular sieve and organic polymer core-shell structure composite adsorbent polymer is uniformly coated, does not affect the pore channel structure of the molecular sieve, has strong hydrophobicity and high stability, and has excellent VOCs adsorption performance under dry and humid conditions.
Description
Technical Field
The invention belongs to the technical field of adsorbents, and particularly relates to a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent.
Background
Volatile Organic Compounds (VOCs) are a general term for volatile organic compounds having a melting point lower than room temperature and a boiling point between 50 ℃ and 260 ℃, and are widely distributed in air, soil and water, and the VOCs are various and mainly include hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ketones, esters and the like. The emission of VOCs mainly comes from industrial sources, mobile sources and living sources, and the emission of VOCs is always increasing in recent years. The kinds of VOCs are complex, which seriously harms the nerve and immune system of human body, causes the problems of respiratory tract infection, nerve disorder and the like, can cause cancer, teratogenesis, mutagenesis and the like, and in addition, most VOCs can form secondary pollution, form photochemical smog and the like, which seriously damages the environmental quality and human health, so the treatment of the VOCs is urgent.
At present, VOCs (volatile organic compounds) control methods mainly comprise an absorption method, an adsorption method, a catalytic oxidation method, a biodegradation method and the like, wherein the adsorption method has the characteristics of simple operation, low cost, high purification efficiency and the like, and becomes one of treatment methods with wide application. The key point of the adsorption method lies in the selection of an adsorbent, the molecular sieve has a unique pore structure, a large specific surface area and good stability, and is an ideal adsorption material, but the surface of the molecular sieve has hydrophilicity, so that the application of the molecular sieve in absorbing VOCs under an aqueous condition is limited, and therefore, the development of a hydrophobic molecular sieve with high adsorption capacity is needed.
Porous Organic Polymers (POPs) are a class of porous materials connected through covalent bonds, and the frameworks of the POPs mainly consist of light elements, so that the POPs have the advantages of low density, adjustable pore structures and the like. The outstanding advantage of POPs as adsorbents is their inherent hydrophobicity, which makes POPs have a great advantage for the adsorption of VOCs under humid conditions. In addition, the structure of POPs containing aromatic hydrocarbons can effectively adsorb toluene through pi-pi bonds. However, POPs have problems of high synthesis cost and poor thermal stability, which limits their application in practical adsorption. In recent years, hydrophobic core-shell structure adsorbents have received much attention. The hydrophobic POPs coated on the surface of the molecular sieve is expected to combine the advantages of the two materials to obtain the VOCs adsorbent with strong hydrophobicity, high thermal stability and low cost.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a composite adsorbent with a molecular sieve and a porous organic polymer core-shell structure.
In order to solve the technical problem, the invention provides a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent, which comprises the following steps:
(1) weighing a certain amount of organosilane, dissolving in an organic solvent, stirring at room temperature for 5-10min, adding a molecular sieve with a certain mass, and performing ultrasonic treatment for 30min to obtain a mixed solution A; in the mixed solution A, the mass ratio of the organosilane to the molecular sieve is 0.1-0.5;
(2) weighing a certain amount of benzyl chloride, dissolving the benzyl chloride in an organic solvent, stirring the benzyl chloride at room temperature for 10 to 20min, and then adding a certain amount of organic cross-linking agent to obtain a mixed solution B; in the mixed solution B, the molar ratio of the benzyl chloride to the organic cross-linking agent is 0.67; the organic cross-linking agent is one or more of benzaldehyde dimethyl acetal, dimethoxymethane and 1, 4-bis (methoxymethyl) benzene;
(3) dropwise adding the mixed solution B into the mixed solution A, stirring at room temperature for 5-10min, then adding a certain amount of anhydrous aluminum chloride, and stirring for 5-10min to obtain a mixed solution C;
(4) transferring the mixed solution C into a round-bottom flask, and stirring for reaction; naturally cooling to room temperature, filtering and recovering a solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at the temperature of 80 ℃, and then performing vacuum drying to obtain the molecular sieve and organic polymer composite adsorbent.
Further, in the step (1) and the step (2), the organic solvent is one of N, N-dimethylformamide, dichloroethane, toluene, N-hexane and cyclohexane.
Further, in the step (1), the organosilane is one of triethoxysilane, trimethoxyphenylsilane, vinyltrimethoxysilane and vinyltriethoxysilane;
the molecular sieve is one or more of X, Y, Beta, ZSM-5, EMT and MCM-48
Further, in the step (4), the stirring reaction conditions are as follows: stirring at 50 deg.C for 1 hr, heating to 60-100 deg.C, and stirring for 8-24 hr.
The invention also comprises the composite adsorbent prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the synthesis method is simple and easy to operate; the synthesized molecular sieve and organic polymer core-shell structure composite adsorbent polymer is uniformly coated, does not affect the pore channel structure of the molecular sieve, has strong hydrophobicity and high stability, and has excellent VOCs adsorption performance under dry and humid conditions.
Drawings
Fig. 1 is an XRD chart of the composite adsorbent of Y molecular sieve and porous organic polymer obtained in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings and specific embodiments, which are only illustrative of the present invention and are not intended to limit the present invention.
Example 1:
a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent comprises the following steps:
the method comprises the following steps: 0.1g of triethoxyphenylsilane is weighed and added into 20ml of dichloroethane, stirred for 10min, added with a 1.0g Y molecular sieve and subjected to ultrasonic treatment for 30min to obtain a mixed solution A.
Step two: 0.13g of benzyl chloride is weighed and dissolved in 30ml of dichloroethane, and after stirring for 10min at room temperature, 0.22g of benzaldehyde dimethyl acetal is added, and stirring is continued for 20min, so that a mixed solution B is obtained.
Step three: and dropwise adding the mixed solution B into the mixed solution A, stirring for 10min, adding 0.2g of anhydrous aluminum chloride, and continuously stirring for 10min to obtain a mixed solution C.
Step four: the mixed solution C was transferred to a round-bottom flask, stirred at 50 ℃ for 1 hour, then warmed to 80 ℃ and stirred for reaction for 12 hours. Naturally cooling to room temperature, filtering and recovering the solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at 80 ℃ for 12 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain the Y molecular sieve and organic polymer composite adsorbent, wherein the structure is not changed as shown in figure 1.
Example 2:
a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent comprises the following steps:
the method comprises the following steps: 0.5g of triethoxyphenylsilane is weighed and added into 20ml of dichloroethane, stirred for 10min, added with a 1.0g Y molecular sieve and subjected to ultrasonic treatment for 30min to obtain a mixed solution A.
Step two: 0.13g of benzyl chloride is weighed and dissolved in 30ml of dichloroethane, and after stirring for 10min at room temperature, 0.22g of benzaldehyde dimethyl acetal is added, and stirring is continued for 20min, so that a mixed solution B is obtained.
Step three: and dropwise adding the mixed solution B into the mixed solution A, stirring for 10min, adding 0.2g of anhydrous aluminum chloride, and continuously stirring for 8min to obtain a mixed solution C.
Step four: the mixed solution C was transferred to a round-bottom flask, stirred at 50 ℃ for 1 hour, then warmed to 80 ℃ and stirred for reaction for 12 hours. Naturally cooling to room temperature, filtering and recovering a solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at 80 ℃ for 12 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain the Y molecular sieve and organic polymer composite adsorbent.
Example 3:
a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent comprises the following steps:
the method comprises the following steps: 0.1g of triethoxyphenylsilane is weighed and added into 20ml of dichloroethane, stirred for 10min, added with a 1.0g Y molecular sieve and subjected to ultrasonic treatment for 30min to obtain a mixed solution A.
Step two: 0.13g of benzyl chloride is weighed and dissolved in 30ml of dichloroethane, after stirring for 10min at room temperature, 0.11g of dimethoxymethane is added, and stirring is continued for 20min, so that a mixed solution B is obtained.
Step three: and dropwise adding the mixed solution B into the mixed solution A, stirring for 10min, adding 0.2g of anhydrous aluminum chloride, and continuously stirring for 10min to obtain a mixed solution C.
Step four: the mixed solution C was transferred to a round-bottom flask, stirred at 50 ℃ for 1 hour, then warmed to 80 ℃ and stirred for reaction for 12 hours. Naturally cooling to room temperature, filtering and recovering a solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at 80 ℃ for 12 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain the Y molecular sieve and organic polymer composite adsorbent.
Example 4:
a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent comprises the following steps:
the method comprises the following steps: 0.1g of triethoxyphenylsilane is weighed and added into 20ml of dichloroethane, stirred for 10min, added with a 1.0g Y molecular sieve and subjected to ultrasonic treatment for 30min to obtain a mixed solution A.
Step two: 0.13g of benzyl chloride is weighed and dissolved in 30ml of dichloroethane, and after stirring for 10min at room temperature, 0.22g of benzaldehyde dimethyl acetal is added, and stirring is continued for 20min, so that a mixed solution B is obtained.
Step three: and dropwise adding the mixed solution B into the mixed solution A, stirring for 10min, adding 0.2g of anhydrous aluminum chloride, and continuously stirring for 10min to obtain a mixed solution C.
Step four: the mixed solution C was transferred to a round-bottom flask, stirred at 50 ℃ for 1 hour, then warmed to 60 ℃ and stirred for reaction for 12 hours. Naturally cooling to room temperature, filtering and recovering a solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at 80 ℃ for 12 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain the Y molecular sieve and organic polymer composite adsorbent.
Example 5:
a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent comprises the following steps:
the method comprises the following steps: 0.1g of triethoxyphenylsilane is weighed and added into 20ml of dichloroethane, stirred for 10min, added with a 1.0g Y molecular sieve and subjected to ultrasonic treatment for 30min to obtain a mixed solution A.
Step two: 0.13g of benzyl chloride is weighed and dissolved in 30ml of dichloroethane, and after stirring for 10min at room temperature, 0.22g of benzaldehyde dimethyl acetal is added, and stirring is continued for 20min, so that a mixed solution B is obtained.
Step three: and dropwise adding the mixed solution B into the mixed solution A, stirring for 10min, adding 0.2g of anhydrous aluminum chloride, and continuously stirring for 10min to obtain a mixed solution C.
Step four: the mixed solution C was transferred to a round-bottomed flask, stirred at 50 ℃ for 1 hour, then warmed to 100 ℃ and stirred to react for 12 hours. Naturally cooling to room temperature, filtering and recovering a solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at 80 ℃ for 12 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain the Y molecular sieve and organic polymer composite adsorbent.
Example 6:
a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent comprises the following steps:
the method comprises the following steps: 0.1g of trimethoxyphenylsilane is weighed and added into 20ml of normal hexane, stirred for 10min, added with a 1.0g Y molecular sieve and subjected to ultrasonic treatment for 30min to obtain a mixed solution A.
Step two: 0.13g of benzyl chloride is weighed and dissolved in 30ml of n-hexane, stirred for 10min at room temperature, then 0.22g of benzaldehyde dimethyl acetal is added, and stirring is continued for 20min, so that a mixed solution B is obtained.
Step three: and dropwise adding the mixed solution B into the mixed solution A, stirring for 10min, adding 0.2g of anhydrous aluminum chloride, and continuously stirring for 10min to obtain a mixed solution C.
Step four: the mixed solution C was transferred to a round-bottom flask, stirred at 50 ℃ for 1 hour, then warmed to 80 ℃ and stirred for reaction for 24 hours. Naturally cooling to room temperature, filtering and recovering a solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at 80 ℃ for 12 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain the Y molecular sieve and organic polymer composite adsorbent.
Example 7:
a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent comprises the following steps:
the method comprises the following steps: 0.1g of trimethoxyphenylsilane is weighed and added into 20ml of normal hexane, stirred for 10min, added with a 1.0g Y molecular sieve and subjected to ultrasonic treatment for 30min to obtain a mixed solution A.
Step two: 0.13g of benzyl chloride is weighed and dissolved in 30ml of n-hexane, stirred for 10min at room temperature, then 0.22g of benzaldehyde dimethyl acetal is added, and stirring is continued for 20min, so that a mixed solution B is obtained.
Step three: and dropwise adding the mixed solution B into the mixed solution A, stirring for 10min, adding 0.2g of anhydrous aluminum chloride, and continuously stirring for 10min to obtain a mixed solution C.
Step four: the mixed solution C was transferred to a round-bottom flask, stirred at 50 ℃ for 1 hour, then warmed to 80 ℃ and stirred for reaction for 8 hours. Naturally cooling to room temperature, filtering and recovering a solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at 80 ℃ for 12 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain the Y molecular sieve and organic polymer composite adsorbent.
Example 8:
a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent comprises the following steps:
the method comprises the following steps: 0.1g of triethoxyphenylsilane is weighed and added into 20ml of dichloroethane, stirred for 10min, added with 1.0g of ZSM-5 molecular sieve and subjected to ultrasonic treatment for 30min to obtain a mixed solution A.
Step two: 0.13g of benzyl chloride is weighed and dissolved in 30ml of dichloroethane, and after stirring for 10min at room temperature, 0.22g of benzaldehyde dimethyl acetal is added, and stirring is continued for 20min, so that a mixed solution B is obtained.
Step three: and dropwise adding the mixed solution B into the mixed solution A, stirring for 10min, adding 0.2g of anhydrous aluminum chloride, and continuously stirring for 10min to obtain a mixed solution C.
Step four: the mixed solution C was transferred to a round-bottom flask, stirred at 50 ℃ for 1 hour, then warmed to 80 ℃ and stirred for reaction for 12 hours. Naturally cooling to room temperature, filtering and recovering a solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at the temperature of 80 ℃ for 12 hours, and then performing vacuum drying at the temperature of 60 ℃ for 12 hours to obtain the ZSM-5 molecular sieve and organic polymer composite adsorbent.
Example 9:
a preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent comprises the following steps:
the method comprises the following steps: 0.1g of triethoxyphenylsilane is weighed and added into 20ml of dichloroethane, stirred for 10min, added with 1.0g of Beta molecular sieve and subjected to ultrasonic treatment for 30min to obtain a mixed solution A.
Step two: 0.13g of benzyl chloride is weighed and dissolved in 30ml of dichloroethane, and after stirring for 10min at room temperature, 0.22g of benzaldehyde dimethyl acetal is added, and stirring is continued for 20min, so that a mixed solution B is obtained.
Step three: and dropwise adding the mixed solution B into the mixed solution A, stirring for 10min, adding 0.2g of anhydrous aluminum chloride, and continuously stirring for 10min to obtain a mixed solution C.
Step four: the mixed solution C was transferred to a round-bottom flask, stirred at 50 ℃ for 1 hour, then warmed to 80 ℃ and stirred for reaction for 12 hours. Naturally cooling to room temperature, filtering and recovering a solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at 80 ℃ for 12 hours, and then performing vacuum drying at 60 ℃ for 12 hours to obtain the Beta molecular sieve and organic polymer composite adsorbent.
From the above examples, it is understood that the above ranges of reaction temperature and reaction time are applicable to the preparation of the composite material. The preparation method has universality, and can synthesize the molecular sieve and organic polymer core-shell structure composite adsorbent for different molecular sieves and different organic solvents.
And (3) testing: the application of the molecular sieve polymer core-shell structure composite material to toluene gas adsorption is represented by an example sample: 0.1g of adsorbent is weighed into a quartz tube reactor of an adsorption device, the adsorbent is pretreated before the adsorption is started, heated at 200 ℃ for 2 hours and purged with nitrogen to remove water and other organic impurities adsorbed in the material. After the pretreatment is finished, the solution is cooled to room temperature for adsorption, the total adsorption flow is kept at 45ml/min, and the initial concentration of the toluene is 1000 ppm. The outlet concentration was detected on-line by gas chromatography, and when the outlet concentration reached 95% of the initial concentration, adsorption was considered to be saturated. The toluene adsorption amount was calculated by the breakthrough curve integral area equation. As a result, the samples in the examples can absorb toluene in an amount of 115-140mg/g (Table 1) under the relative humidity condition of 30%, which is at least 36.2% higher than the toluene absorption under the humidity condition reported in the literature. The composite material adsorbent formed by the method has excellent adsorption performance.
Therefore, the polymer layer is coated on the surface of the molecular sieve, the influence of water vapor on the toluene adsorption performance is weakened, and the composite material still has good toluene adsorption capacity under the relative humidity condition. In addition, the pi-pi interaction between the benzene ring in the polymer layer and the toluene molecule enhances the toluene adsorption capacity of the composite material.
TABLE 1 adsorption of toluene on the samples of the examples under dry and humid conditions
Although the present invention has been described in connection with the accompanying drawings, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than restrictive, and many modifications and variations may be made by those skilled in the art without departing from the spirit of the present invention while the invention is taught.
Claims (7)
1. A preparation method of a molecular sieve and porous organic polymer core-shell structure composite adsorbent is characterized by comprising the following specific steps:
(1) weighing a certain amount of organosilane, dissolving in an organic solvent, stirring at room temperature for 5-10min, adding a molecular sieve with a certain mass, and performing ultrasonic treatment to obtain a mixed solution A; in the mixed solution A, the mass ratio of the organosilane to the molecular sieve is 0.1-0.5;
(2) weighing a certain amount of benzyl chloride, dissolving the benzyl chloride in an organic solvent, stirring the benzyl chloride at room temperature for 10 to 20min, and then adding a certain amount of organic cross-linking agent to obtain a mixed solution B; in the mixed solution B, the molar ratio of the benzyl chloride to the organic cross-linking agent is 0.67;
(3) dropwise adding the mixed solution B into the mixed solution A, stirring at room temperature for 5-10min, then adding a certain amount of anhydrous aluminum chloride, and stirring for 5-10min to obtain a mixed solution C;
(4) transferring the mixed solution C into a round-bottom flask, and stirring for reaction; naturally cooling to room temperature, filtering and recovering a solid phase product, washing with methanol for multiple times, performing Soxhlet extraction at the temperature of 80 ℃, and then performing vacuum drying to obtain the molecular sieve and organic polymer composite adsorbent.
2. The preparation method of the molecular sieve and porous organic polymer core-shell structure composite adsorbent according to claim 1, wherein the organic cross-linking agent is one or more of benzaldehyde dimethyl acetal, dimethoxymethane, and 1, 4-bis (methoxymethyl) benzene.
3. The method for preparing the composite adsorbent with the molecular sieve and the porous organic polymer core-shell structure according to claim 1, wherein in the step (1) and the step (2), the organic solvent is one of N, N-dimethylformamide, dichloroethane, toluene, N-hexane and cyclohexane.
4. The method for preparing the composite adsorbent with the molecular sieve and the porous organic polymer core-shell structure according to claim 1, wherein in the step (1), the organosilane is one of triethoxysilane, trimethoxyphenylsilane, vinyltrimethoxysilane and vinyltriethoxysilane.
5. The preparation method of the composite adsorbent with the molecular sieve and the porous organic polymer core-shell structure according to claim 1, wherein the molecular sieve is one or more of X, Y, Beta, ZSM-5, EMT and MCM-48.
6. The preparation method of the composite adsorbent with the molecular sieve and the porous organic polymer core-shell structure according to claim 1, wherein in the step (4), the stirring reaction conditions are as follows: stirring at 50 deg.C for 1 hr, heating to 60-100 deg.C, and stirring for 8-24 hr.
7. A composite adsorbent obtained by the production method according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110338859.3A CN113198433B (en) | 2021-03-30 | 2021-03-30 | Molecular sieve and porous organic polymer core-shell structure composite adsorbent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110338859.3A CN113198433B (en) | 2021-03-30 | 2021-03-30 | Molecular sieve and porous organic polymer core-shell structure composite adsorbent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113198433A true CN113198433A (en) | 2021-08-03 |
| CN113198433B CN113198433B (en) | 2022-11-11 |
Family
ID=77025831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110338859.3A Active CN113198433B (en) | 2021-03-30 | 2021-03-30 | Molecular sieve and porous organic polymer core-shell structure composite adsorbent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113198433B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB480592A (en) * | 1936-07-24 | 1938-02-24 | Ig Farbenindustrie Ag | Plasticisers for vinyl resins |
| GB567807A (en) * | 1943-07-21 | 1945-03-05 | Frederick Robert Basford | Triphenylethylene derivatives |
| CN105251441A (en) * | 2015-11-12 | 2016-01-20 | 环境保护部华南环境科学研究所 | High-performance mesoporous-micro double hole controllable molecular sieve adsorbent and preparation and application thereof |
| CN109433157A (en) * | 2018-09-28 | 2019-03-08 | 天津大学 | Catechol modified mesoporous silicon adsorbent, its preparation method and use |
-
2021
- 2021-03-30 CN CN202110338859.3A patent/CN113198433B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB480592A (en) * | 1936-07-24 | 1938-02-24 | Ig Farbenindustrie Ag | Plasticisers for vinyl resins |
| GB567807A (en) * | 1943-07-21 | 1945-03-05 | Frederick Robert Basford | Triphenylethylene derivatives |
| CN105251441A (en) * | 2015-11-12 | 2016-01-20 | 环境保护部华南环境科学研究所 | High-performance mesoporous-micro double hole controllable molecular sieve adsorbent and preparation and application thereof |
| CN109433157A (en) * | 2018-09-28 | 2019-03-08 | 天津大学 | Catechol modified mesoporous silicon adsorbent, its preparation method and use |
Non-Patent Citations (1)
| Title |
|---|
| SHUANGCHUN LU ET AL: "Core-shell structured Y zeolite/hydrophobic organic polymer with improved toluene adsorption capacity under dry and wet conditions", 《CHEMICAL ENGINEERING JOURNAL》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113198433B (en) | 2022-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2002500549A (en) | Coated fiber substrate | |
| CN106795180A (en) | The mixed substrate membrane containing nano-grade molecular sieve of the modified and prepared therefrom azide crosslinking of zeolite imidazole ester skeleton | |
| CN110218301A (en) | One kind being based on the organic microporous polymer of conjugation and preparation method thereof of 1,3,5- tri- (4- Fonnylphenyl) benzene | |
| CN112371083B (en) | Method for compounding hydrophobic coating on surface of activated carbon | |
| CN113372524B (en) | Non-reversible thiourea-linked covalent organic framework capable of rapidly removing mercury, and preparation method and application thereof | |
| US8530375B2 (en) | Regenerable solid imine sorbents | |
| CN113683740A (en) | Halogen ion functionalized organic porous material and preparation method and application thereof | |
| Qin et al. | Zinc-based triazole metal complexes for efficient iodine adsorption in water | |
| CN106111086B (en) | A kind of absorption Pd2+Ionic polymeric sorbent of metal ion and preparation method thereof | |
| CN113769715B (en) | Yttrium-based metal organic framework material and preparation method and application thereof | |
| CN114939431A (en) | CN@ZrO 2 Composite material and application thereof in catalyzing CO 2 Application in cycloaddition reaction with epoxide | |
| CN113198433B (en) | Molecular sieve and porous organic polymer core-shell structure composite adsorbent and preparation method thereof | |
| EP2907569B1 (en) | Regeneration method for cu-btc material | |
| CN109012029B (en) | Carbon dioxide adsorption recovery method | |
| CN111454455A (en) | Porous hybrid polymer rich in POSS (polyhedral oligomeric silsesquioxane) derived silicon hydroxyl and preparation method and catalytic application thereof | |
| CN116832781A (en) | Preparation method and application of solid amine adsorbent | |
| CN111302356A (en) | Preparation method of hydrophobic Y-type molecular sieve and hydrophobic Y-type molecular sieve | |
| CN115487789A (en) | Preparation method of adsorption resin for volatile organic compound purification | |
| CN113967461B (en) | Porous carbon material rich in amino groups and preparation method and application thereof | |
| CN115350689A (en) | Preparation method of IL @ MOF composite material and application of IL @ MOF composite material in gas adsorption separation | |
| CN109320732B (en) | Adamantyl porous polymer with high specific area and preparation method thereof | |
| CN110694593A (en) | Preparation method of cyclodextrin adsorption material | |
| CN115337913B (en) | Catechu [9] arene, and preparation method and application thereof | |
| CN115025812B (en) | Nano MnO X -VO X /TiO 2 -modified molecular sieve composite catalyst and preparation method and application thereof | |
| CN110681348A (en) | Dealuminization modification method of Y molecular sieve applied to acetone adsorption |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |